Process for resolving petroleum emulsions



Patented July 18, 1939 PROCESS FOR RESOLVING PETROLEUM EMULSIONS' No Drawing. Application May 31, 19 38, Serial No. 211,039

7 Claims.

This invention relates to the treatment of emulsions of mineral oil and water, such as petroleum emulsions, and has for its object to provide a. novel process for resolving or breaking petroleum emulsions of the water-in-oil type into their component parts of oil and water or brine.

The treating agent or demulsifying agent em ployed in the present process is 'a new composition of matter consisting of a certain kind of complex amine derived by reaction between (a) acid esters obtained from phthalated monoricinolein, phthalated diricinolein, phthalated mono-olein, phthalated di-olein, phthalated mononaphthenin, phthalated monoabietin, or similar materials; and (b) simpler amines of the kind hereinafter described, and the process involves subjecting a petroleum emulsion of the water-in-oil type to the action of said demulsifying agent, so as to cause the emulsion to break down and separate into its component parts of oil and Water or brine when the emulsion is permitted to remain in a quiescent state after treatment or is subjected to other equivalent separatory procedures.

Inasmuch as the demulsifying agent employed in my process'constitutes a new chemical compound or new composition of matter, I deem it advisable to describe the raw materials entering into the manufacture of the same, as well as the method of manufacture.

One can obtain or manufacture chemical compounds whose composition is indicated by the following formulas:

The compounds above described may be summarized by the following formula:

(R.COO.C2H-l)m in which m represents the number 1 or 2, m represents the number 1 or 2, and m represents the number or 1, with the proviso that m-i-m'+m=3 However, the radical C2H4 which appears i1%he above formula may represent any similar rad al, such as a CaHe radical, C4H8 radical, etc., and therefore, the above formula may be rewritten:

nooocnnmm (ottoman);

' where n represents a small whole number, prefradical, such as a methyl, ethyl, propyLamyl, or

similar radical; or T may represent a non hydroxy alicyclic radical, such as a cyclohe'xyl radi-/ cal, or a non-hydroxy aralkyl radical, such as a benzyl radical; or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid, such as acetic acid, butyric acid, heptoic acid, or the like, all of which are characterized by having less than 8 carbon atoms. The alkylol radical prior to acylation may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided the hydroxy radical is attached to the aliphatic residue of the aralkyl radical.

In the above formula, R.COO represents the oxyacyl or acid radical derived from the acid R.COOI-I. R.COOH. represents any monobasic detergent-forming carboxy acid, such as a typical These acids combine with alkali to produce soap or soap-like materials and are commonly referred to as being monobasic detergent-forming carboxy acids. Blown oils (oxidized oils) are not included. k

The alkylol radical previously referred to prior to esterification may be a hydroxy alicyc ic or a hydroxy aralkyl radical, provided the hydroxy radical is attached to the aliphatic residue of the aralkyl radical.

As to the amines above described, which happen to be tertiary amines, it may be well to point out that, these may be formed readily by erection involving an ester of the selected detergent-forming acid, for instance, a fatty acid ester, such as may be illustrated in the followingmanner:

tertiary amines illustrated. Reference is made to co-pending application for patent Serial No. 206,904; filed May 9, 1938, by De Groote, Kaiser and Blair.

In the remaining type of material there is an amino hydrogen atom present. Thema'nufacture of such material may by illustrated by the following reactions:

OHCflh However, if maximum yields are not necessary, one need not resort to reactions of the kind previously described to produce secondary amines,

but one may employ the following type 01' re- Suitable primary and secondary amines which.

may be employed to produce materials of the kind The expression 2,160,434 the glyceride, and a corresponding amine. This above described include the following: diethanolamine, monoethanolamine, ethyl ethanolamine, methyl ethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc. Other examples include cyclohexylolamine, dicyclohexylolamine, cyclohexyl ethanolamine, cyclohexyl propanolamine, benzylethanolamine;benzylpropanolamine, pentanolamine, hexanolamine, octylethariolamine, octadecyiethanolamine, cyclohexanolethanolamine, etc.

Similarly, suitable tertiary amines which may -be employed include the following: triethanob CQH40H Such amines may serve as functional equivalents of the previously described amines and which are free from an ether linkage.

All of the amines of the kind above described and characterized by the formula:

(R.OO0.0||H:)-'n

in which m represents the number 1 or 2,-m',

represents the number 1 or 2, and m" represents the number 1, with the proviso that and n represents asmall whole number, preferably riot over 10, have four common characteristics. In the first place, these amines are not quaternary ammonium bases or salts thereof. "quaternary ammonium is properly and conventionally applied to compounds in which all four hydrogen atoms of the ammonium radical NH4 have been replaced by a hydrocarbon radical or oily-hydrocarbon radical, as, for example, in trimethyl phenyl ammonium hydroxide.

Secondly, an important characteristic which must be recognized is, that these amine compounds are not amides. It is to be noted that an amide formation involves a product in which'there is a direct linkage between the carboxylic carbon atom and the nitrogen atom in the amine. This is not the case in the compounds employed as intermediate raw materials for production of the compounds used as demulsifying agents in the present process.

In the third place, it must be recognized that these compounds are derived only from basic amines. The word basic is employed to exclude amines having little or no basicity, such as the ordinaryaromatic amines or any amine having at least one aryl radical directly joined to the amino nitrogen atom. For this reason, these amine products which are herein. contemplated as demulsifying agents and which necessarily are characterized by freedom from any aryl groups as such, cannot be derived from aryl amines. They are derived solely from alkyl, alicyclic, or aralkyl amines having at least one hydroxyl group present. It is true that in the aralkyl amines there is an aryl group present, but it is not directly attached to the nitrogen atom, as in the case of aryl amines, but in fact, represents nothing more or less than a substituted alkyl amine. F01 instance, I consider benzylamine as being the primary amine, phenmethyl amine.

Finally, it must be recognized that these materials have not lost any basicity in the forms of the esterified amine, and that. they exhibit all the properties of a basic amine, that is, they combine with water to form a base presumably a substituted ammonium compound, but not quaternary ammonium compound insofar that there are always one, two, or three unsubstituted hydrogen atoms of the ammonium radical present. They combine with various acids to form salts. For example, they may be combined with acetic acid, hydrochloric acid, lactic acid, chloracetic acid, nitricacid, butyric acid, phosphoric acid,

oxalic acid, or any suitable organic or inorganic acid, to form salts. It is understood that the reference in the specification and appended claims to the amines includes the basic form and the acid salts as well as the amines themselves. The characteristic demulsifying properties of the new compositionsv of matter herein described arecontributed in part by the amine, and it is immaterial whether the amine may be considered as being in any one of the following forms:

in which T represents the substituents for the amino hydrogen atoms of the parent ammonia from which all amines are hypothetically derived, and X simply represents the acid radical of any acid' employed. This statement applies with equal force and effect to the final product, or compos'ition of matter, which is also a basic amine of a more complex type.

Reference is again made to the formula which QLsummarizes the various amines used as intermediate raw materials, viz.:

(acooonnmm OH.Cy HZn)III' in which the characteristics have their previous significance.

Attention is directed to the fact that where the substituted alkyl radical OH.R.COO.C2H4- appears, a suitable non-aryl radical other than an aliphatic residue may serve as the functional equivalent; for instance, an alicyclic radical derived from a cyclohexyl radical, or an aralkyl radical derived from a benzyl radical. words, .inthe hereto appended claims reference to the CnHZn radical as such, or as an alkyl'radical or residue is intended in the broad sense to include the alicyclic radicals or residues, -or the arallgyl radicals or residues which are the equivalent thereof. There is no intention to include an aromatic radical where there is a direct linkage,

between the aromatic nucleus andthe amino hydrogen atom, for the reason that such products have little or no basicity and do not have the characteristic properties of the amines previously.

described.

In indicating the various hydroxylated tertiary amines of the non-aryl type which may be employed to produce the amine contemplated as the demulsifying agent of the present process,

it is desirable to indicate that amines ofthe type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxyl radical of the hydroxy tertiary amine, are not included within the broad class of hydroxy tertiary amines, unless there is another hydroxyl radical attached to the usual alkyl radical. For instance, if ethyl diethanol- In other amine is treated with two moles of lactic acid so as to form the dilactyl compound of the following formula:

not represent a hydroxy tertiary amine within the meaning or scope, as herein .employed. If,

on the other hand, trietha'nolamine were treated with lactic acid,v so as to give monolactyl tri-- ethanolamine of the following composition:

crnono-w-orm OHC2Hr- N orioin i then such compound would be inclined, due to the presence of one or more hydroxyl radicals attached to the alkyl radicals.

Similarly, in indicating the various hydro ylated primary or secondary amines of the nonaryl type which may be employed to produce the amine contemplated as the demulsifying agent of the present process; it is-desirable toindicate that amines of the type where a hydroxy acyl radical replaces a hydrogen atom of the hydroxyl radical of a hydroxy primary or secondary amine, are not included within the broad class of hydroxy tertiary amines, unless there is'another hydroxyl radical attached to the usual alkyl radical. For instance, if ethanolamine is treated withlactic acid so as to form the lactyl deriva-' tive of the following formula:

on o

0H3on.o--o--o2H.NHH

same would be true if the corresponding product were derived from diethanolamine, provided both hydroxy radicals had been esterifled with lactic acid.

The manufacture of compounds from tertiary amines is relatively simple, because no precautions are necessary to prevent amidiiication. The selected detergent-forming acid, or ester, as, for example, a fatty oil and the selected hydroxy tertiary amine are mixed in suitable proportions and heated at some point above the boiling point 01 water, for instance, 110 C., and at a point below the decomposition point of the amine or the fatty oil, for instance, 180 C., for a suitable period of time, such as two to eight hours. Mild agitation is employed. A catalyst such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about onehalf of 1% or less. It is noted that the fatty acids are employed in this instance in the form of an. ester, to wit, the glyceride, although, as previously pointed out, other functional equivalents can be readily employed with equal facility. It is to be noted that the reactions above described do not take place to any appreciable extent if the fatty acid has been converted. into the soap or salt. -Such salts are not functional 2 equivalents. As previously indicated, an ester of abietic acid might be employed if desired.

when, however, one is employing a hydroxy secondary amine, precautions must be taken, so that one gets a substantial percentage of products derived by esterification, rather than amidification. Any suitable ester may be employed, but

' it is often most convenient to employ the glyceride ot a fatty acid, fordnstance, trirlcinolein.

The selected glyceride and the selected hydroxy secondary amine are mixed in suitable proportions and heated at some point above the boiling point of water, for instance, 110 C., and below the decomposition point of the amine or fatty material, for instance, 180.C., for a suitable period of time, such as 4-24 hours. Mild agitation is employed. -A catalyst such as sodium oleate, sodium carbonate, caustic soda, 'etc., may be present in amounts of about or less. It is to be noted that-the fatty acids are present in ester foi' n and not in the form of the free acid,

and thus there is no tendency to form the salt Intermediate amine-E:rample 1 Castor ,oil is employed. For sake of convenience, its molecular weight is considered as being 925. Commercial triethanolamine and castor oil in the proportion of one mole of castor oil and three moles of triethanolamine are heated to a temperature between ISO-180 C. for two hours.

Mild agitation is-employed. The reaction product so produced may be used as such, or may be converted into the acetate or other suitable'form.

' lntermedicte aminelt'xample 2 The same procedure is followed as in Intermediate amine Example 1, except that the'ratio employed is two moles of the castor oil to three moles of triethanolamine.

Intermediate amine-Example 3' One mole of methyl naphthenate is reacted in the manner previously described with one of triethanolamine.

Intermediate amine Example 4 Diethanolamine is substituted for triethanolamine in Example 3.

thenate in Examples 3 and 4 above.

Intermediate amine-Example 6 Olive oil is substituted for castor oil in Examples 1 and 2 above.

Intermediate amine,Ea:ample 7 Ethyl diethanolamine is substituted for triethanolamine in previous examples where triethanolamine has been employed, but ratios are changed, if required, so that there is always one -iion-esterified ethanol radical present.

Intermediate amine-E:rample 8 Cyclohexyl diethanolamine is substituted for triethanolamlnein previous examples where triethanolamine has been employed, but subject to the same modification as indicated in Example '7 immediately preceding.

Intermediate amine-Example 9 Benzyl diethanolamine is substituted for triethanolamine in previous examples where it has been employed. See modification noted in Examples '7 and 8 immediately above.

Intermediate amine-Example 10 Castor oil (triricinolein) is employed. For convenience its molecular weight is considered as being 925. Commercial diethanolamine and castor oil in the proportion of one mole of castor oil to three moles of diethanolamine are heated to a temperature oi 120-140" C. for about twelve hours. Mild agitation is employed. Loss of basicity is an indication of amidification. Time of esteriiication may be extended or temperature lowered or raised'so' as to insure maximum esterification, and particularly so as to produce a product characterized by the presence of one unesterifled alkylol radical attached to the amino nitrogen. The reaction product so produced may be used as such, or may be converted into the acetate or other suitable form.

Having prepared the relatively simpler intermediate amines of the kind previously described, the second step in the preparation of the new composition of matter is to produce acidesters mole of the kind obtainable by reaction between polybasic carboxy acids. or their functional equivalents, suchas the anhydrides and esters, of detergent-forming acids or the like. Detergent-form ing acids are monobasic carboxy acids, such as typical fatty acids, abietic acids, or naphthenic acids. Typical fatty acids are those which occur in naturally-occurring oils and fats and generally have 8 or more carbon atoms and not over 32 carbon atoms. Common examples include oleic acid, stearic acid, linoleic acid, linolenic acid, ricinoleic acid, erucic acid, palmitic acid, myristic acid, etc. These various acids combine with alkali to produce soap or soap-like materials and are commonly referred ,to as being monobasic detergent-forming acids. Blown oils (oxidized oils) are not included. 4

areasse Detergent-forming acids combine with poly-r hydric alcohols to give esters characterized by the presenceof at least one hydroxyl radical attached to the radical which replaces the carboxylic hydrogen. Polyhydric alcohols include glycerol, ethylene glycol, propylene glycol, and other similar glycols, and also a polyhydroxy ether alcohol type of material such as diethylene glycol, diglycerol, triglycerol, etc. Such materials, whether produced from glycerol or from glycol or from two dissimilar polyhydric alcohols, are characterized by the fact that dehydra-. tion produces an oxygen linkage between two organic residues, and thus the material, in addition to having the properties of a polyhydric alcohol, has to some degree at least, the properties of an ether.

As to the manufacture of esters from an alcohol, including polyhydric alcohols, and a carboxy acid, the usual procedure is esterification' in presence of dry hydrochloric acid gas! Such method is satisfactory, provided conditions are controlled so that complete esterification does not take place, and thus result in a material con-- taining no free hydroxyl in the polyhydric alcohol residue. For example, if diglycerol is esterified with four molecules of ricinoleic acid, the resultant product will not contain a free hydroxy group in the polyglycerol residue. However, if esterification is continued so that one, -two or three ricinoleic acid residues are introduced, and so that three, two, or one free hydroxyl residues remain in the polyglycerol radical, then a suitable compound is produced. Esteriflcations to produce the desired product may be conducted in the conventional manner, usually employed in such reactions.

It is, of course, obvious that esters may be produced as readily from naphthenic acid or abietic acid or the like, as from fatty acids. For sake of brevity, reference will be made particularly to fattyacids. A large number of materials derived from fatty acids and characterized by the presence of a free hydroxyl attached to the hydrocarbon radical which replaces the carboxylic hydrogen, is available in the open market and sold under the name of superglycerinated 'fats.

Such materials are used as emulsifying agents,.

both in edible and non-edible products. They are derived from a wide variety of acids and a wide variety of polyhydricalcohols of both the ether type and the non-ether type.

The following formulas indicate the types derivable from non-hydroxylated monobasic carboxy acids:

R.OOO.CaHa

ncoo oanioolm on R.C00.'G:Ha

com,

If such products are reacted with carboxy acid or the anhydride, as, for example,

phthalic acid or phthalic anhydride, one can obtain a large number of esters which are acidic esters in the sense that'there is present a. free carboxyl radical. In the following formulas, no attempt is made to show phthalic anhydride as the usual ortho compound, ,but it is shown as a; para compound, purely for the sake of convenience. The selection of phthalic acid is purely for purposes of illustration. Any one 01' a num-" ber of other acids may be employed.

R.COO.CaHa

GOOD.

Dog COOK aoooc m ooc coon ooo aooomm aoooclmooc (acooilolmo cim OOOH coon' aooomm If, however, such materials were derived from hydroxylated fatty acids without involving the the polybasic- 1| radical and alsothe hydroxyl attached to the radical, then the above formula would appear as follows:

ooccoon on.n.coo.cim

on oocOcoon 011.11.000.00!

ooo

ooc 011.12.000.00?

oocOooon wanoomwanoooOcoOn on.a.coo.c, m.ooccoon A on waacooncino clm 1 00060061: ooccoon onnzcoohcano can 000600011 00000003 on.n.coo.c,n

\\ on ociih However, if one considers the reactions in which only the alcoholiiorm hydroxyl of the. fatty acid radical, for example, ricinoleic acid, is involved in formation of the reaction products obtained, then they may be indicated by the fol- .Bimilarly,-one may have products in which both the 100110110 Didi-0H1 attached to the fatty glycerol or glycol radical are reacted with phthalie anhydride or its equivalent, so as to produce reagents indicated by the following formulas:

accommoocOcoon COOH CODE

COVOH' In the examples shown above, where the ester is polybasic, one might remove the acidity of one of the carboxylic hydrogen atoms or two of the carboxylic hydrogen atoms in any feasible mannet, that is, by neutralization with an alkali or by conversion into an'ester involving a reaction with any suitable alcohol, i. e., a monohydric,

-trihydric, etc. In any event, however, the material derived by reaction between a polybasic acid or its functional equivalent and the hydroxylated ester type of fatty material of the kind described, is always characterized by the presence of at least one free carboxyl radical.

Where reference is made to ricinoleic acid, hydroxystearic acid, abietic acid, and the like, it

isevident that certain simple derivatives, such as the halogenated compounds, are the obvious functional equivalents; for instance, chlorinated recinoleic acid, may be employed instead of ricinoleic acid;..cbrominated oleic acid might be employed instead of oleic acid; hydrogenated abietic acid might be employed instead of abietic acid. In these instances the monobssic detergent-forming carboxy material, notwithstanding modifications of the kind indicated, still has the same functional properties as the unmodified material; and thus acts in the. same manner,-as

far as chemical reactions notedare concerned,

and also as far as producing an' effective demulsiiying agent is-concerned.

In the hereto appended claims, reference to monobasic detergent-forming carboxy acids includes such obvious functional equivalents. As to the manufacture of reagents from polybasic carboxy acids and s'uperglycerinated fats or the like, it need simply be stated that these reagents have been produced and used in the arts as plasticizers, demulsifying agents, etc.; and that the method of producing the same is well known. Briefly stated, esteriiication takes place readily on the application of heat, and the reaction may be hastened by employing a higher temperature,

provided the decomposition does not take place; or the reaction may be conducted in presence of an inert solvent, such as xylene, which may be removed after completion of reaction. The reaction can be hastened also by passing through the mixture a dried inert gas; or the reaction may be conducted under a reflux condenser using material such as xylene and a water trap, so as to remove water as quickly as formed. Generally speaking, however, the reactions take place rapidly, quickly, and completely by simply heating the products together in stoichiometric proportions at a temperature somewhere above the boiling point of water, and particularly at a temperature of about 110-160 C., provided there is no decomposition. Phthalic acid is particularly suitable, because it does not decomposereadily, whereas, some other acid, such as oxalic acid, may be equally desirable, but the temperature of esterification must be lower, of course, to prevent decomposition.

The polybasic acids which may be employed, including some having at least three carboxyl radicals, are phthalic, succinic, malic, fumaric,

citric, maleic,adipic, tartaric, glutaric, diphenic, naphthaliaoxalic; etc.

It is to be noted that the manufacture of the composition of matter in reality involves three different esterification reactions. For example, a fatty acid may be reacted with a tertiary hydroxyamine to 'give products of the kind indicated. Naturally, if the tertiary amine,- such as triethanolamine, is reacted with a glyceride, the reaction may, in essence, be a rearrangementreaction, rather than an esterification reaction, although for purposes of classification, it may be considered as an esterification reaction. The second esterification-reactlon involved is the one between the hydroxy fatty body of the kind de scribed, such as supergiycerinated fats and phthalic anhydride, or the like. Monoabietin or mononaphthenin, of course, may be considered broadly as a superglycerinated fat.

The third esterification reaction is between the two types of materials above described, the simpler amine always being characterized by the presence of an alcoholic hydroxyl radical, and the ester being characterized by the presence of the carboxyl group. The last mentioned esterification reaction goes readily and is nothing more or less than a conventional esterification reaction and requires no further elaboration.

Composition of matte1'--E:ramplev 1 One employs an intermediate amine of the kind described under Intermediate amine-Example labove. Commercial diricinolein is treated with two moles of phthalic anhydride, so as to yield an ester having two free carboxyl radicals. One molecular weight of this acidic ester is reacted with one mole of material exemplifiedby Intermediate amine'Example 1, so as to yield a product characterized by the presence of both free carboxyl radicals and free alcoholic hydroxyl radicals. tion reaction, and the materials-are intermittently mixed and heated at approximately 120160 C. with constant agitation until samples taken from the batch and analyzed show substantially complete reaction. A suitable solvent may be present, and water formed may be distilled ofi continuously during the'esterlfication process. The solvent may remain behind in th final product or be removed, if desired.

This is a conventional esterifica' Diphthalated mono-olein is substituted for dlphthalated diricinolein in Composition of matter-Example 1, immediately above.

Composition of matterE:vample 3 Dimaleated monostearin is substituted for d iphthalated diricinolein in Composition of matterExample 1 above.

Composition of matter-Example 4 Dioxalated mono-abietin is substituted for diphthalated diricinolein in Composition of matter-Example 1 above.

Composition of matter--Example 5 Composition, of matter--Example 6 An amine of the kind characterized by the product described under Intermediate amine- Example 10 is subtsituted in the above Composition of matter-Examples 1-5 for the intermediate amine therein employed.

It should be noted, however, that this particular product contains only two hydroxyl radicals available for esterification per atom of nitrogen. Insofar that some amidification may take place in following the directions in preparing the amine from diethanolamine in Intermediate amine Example 10 above, it is probably the safest procedure to determine the acetyl or hydroxyl value before reacting in molecular proportions.

Attention is directed .to the fact that the alkylolamines are obtained in such a manner that they may be looked upon as being derivatives of dihydric alcohols, for instance, the chlorhydrin of the dihydric alcohol, as indicated in the following manner:

- As previously stated, the C2H4 radical may be any 'the like, as indicated by the following reaction:

It is not necessary to point out that the same types of reactions will produce secondary or tertiary amines and that the reaction is not limited to a combination with ammonia, but may take place with a combination of other primary or secondary amines, such as amylamine, diamylamine, cyclohexylarnine; dicyclohexylamine, benzylamine, .dibenzyiamine, amine, etc.

This means that in the type of material previously described, there is a wide variety of materials, such as monoglycerylarnine, diglycerylamine, monoglyceryl diethylamine, monoglyceryl dipropylamine, diglyceryl propylamine, triglycerylamine, etc, which are functional equivalents of the various amines previously described for reaction with ,triricinolein and the like. When such amines are employed instead of the radical C1.Hz' n appearing in a compound, one would have in place thereof the radical Y-OH.C3H5: or in case the hydroxyl radical of these -O H.CaH5 radical had been removed by esterification with any available carboxyl, then the substituent which replaces the -C1;H2n radical might amylcyclohexylhas been said here in regard to functional equivalents will be perfectly obvious without further explanation to those skilled in the art. See United States Patent No. 2,091,704, dated August 31, 1937, to Duncan and McAllister, and also United States Patent No. 2,042,621, dated June 2, 1936, to Olin. Similarly, it is evident that where reference is made to phthalic acid, some simple derivative, such as chlorinatedphthalic acid, brominated phthalic acid, methylated phthalic acid, or the like, would simply act as a functional equivalent. This applies not only to phthalic acid,'-but all the dibasic acids enumerated. v Similar1y, it is evident that there is no intention to difl'erentiat'e between isgmeric forms. One isomeric form may serve as well as another. Attention particularly called to the last two examples above, which are characterized especialiy by the presence of a free carboxyl radical other than the carboxyl radical derived from dibasic acid. Needless to state, in the reaction between the ester derived by reaction between a polybasiccarboxy acid material and a selected fatty material of the kind described, if there be a carboxyl radical attached'to a fatty chain available for esterification as well as a carboxyl attached to the dibasic acid, then in such event, if there are sumcient available hydroxyl radicals attached the amine of the kind previously described, both types of carboxyl radicals, i. e., (a) a carboxyi radical attached to a polybasic carboxy acid residue; and (b) a carboxyl radical attached to a fatty acid residue may enter into the reaction. However, my experience is that the carboxyl radical attached to the polybasic carboxy acid residue-is generally more reactive andenters into reaction in preference to the other type of carboxyl radical,-although both reactions may take place simultaneously to at least a limited degree.

I desire to emphasize that the products obtained in the above examples may beusedin the form of the amine by direct-contact with an emulsion without contact with water. It may be contacted with Water, i. e., in the form of a solution so as to produce in a greater or lesser hydrogen atom may bereplaced by a suitablev metallic atom, or'an organiceradical derived from an alcohol orfrom an amine. All such ioni'zable hydrogen atom equivalents are considered as the functional equivalent of the ionizable hydrogen atoms themselves, and such neutralized forms are included in thescope ofthe appended claims as the equivalents of the acidic form. -'1'he expression "fatty acid'compound is employed to include the acid itself,

as well as salts and esters thereof. It is realized that where a free mom and a, basic amine residue exist in the samemolecule, there may be a tendency towardsthe formation ofinner salts comparable tosulfanilic acid; but due tothe size of the molecule involved, and perhaps for reasons of steric hindrance, I am not aware that such inner salts are formed.

Briefly, then, the preparation of the composition of matter hereincontemplated depends on a reaction involving a polybasic carboxy acid be indicated bythe formula -D.C3H5-. All that body, or its functional equivalent, as described, and the complex amine of the kind described, in such a manner as to involve reactions other than salt formation. In other words, the complex amines are basic in nature, and therefore, could react with a polybasic acid to form a salt in a manner which, for sake of convenience, will be indicated by a somewhat simpler reaction, thus:

coon

. claims, refers not only to the acid itself, but to any functional equivalent, such as the anhydride, the acyl chloride, a salt form having at least two free carboxyls, such as mono-sodium citrate, etc. It is also understood that in the hereto appended claims the nature of the final product is not limited to the form having a free carboxylic hydrogen, but that such free carboxylic hydrogen may actually be replaced by any functional equivalent of the kind previously described, for instance, a metallic atom, an ammonium radical, an amine radical, such as an amylamine radical, benzylamine radical, ethanolamine radical, diethanolamine radical, triethanolamine radical, a hydrocarbon radical, such as an ethyl, methyl, propyl, or amyl radical, a radical derived from ethylene glycol, glycerol, or 'the like; a cycloehexyl radical, benzyl radical, etc. All such forms in which such ionizable hydrogen atom equivalent replaces an ionizable hydrogen atom, are obvious functional equivalents.

Attention is directed to the fact that the word "amidification has been applied to the reaction involving the replacement of an amino hydrogen amide or the formation of an imide or substituted I Such obvious departure from conven-' imi'de. tional nomenclature has been .for purposes of simplicity and to showthe similarity between certain reactions.

It is desirable to emphasize again that in the hereto appended claims reference to a polybasic carboxy acid includes not only the acid itself, but also various salts and esters thereof, and also other functional equivalents, such as the anhyhereto appended claims, reference to the product derived by reaction between an acid ester of the kind previously described and an amine of the kind previously described, is meant torefer to drides, acyl chlorides, etc. Furthermore, in the such products in all its various modifications previously referred to, to wit, such instances where form; as, for example, obtainable by contact with water. The functional equivalents of all these variations have been pointed out previously and were readily comprehended; and the scope of the claims, in the light of such obvious equivalents,

requires no further discussion.

As to blown oils, blown fatty acids, polymerized oils, polymerized fatty acids, and other similar materials obtained by oxidation, it is not intended that they should be reacted with .amines to produce the intermediate amine, which, in turn, is reacted with the acidic ester derived, in part, from a polybasic carboxy acid.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent,

ilarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limited water solubility and relatively limited oil solubility. However,. since such reagents are sometimes used in a ratioof 1 to 0, 00, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

I desire to point out that the superiority of the reagent or demulsifying agent-contemplated in my process is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that theparticular demulsifying agent or treating-agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but I have found that such a demulsifying agent has commercial value, as' it will economically break or resolve oil field emulsions in a number of cases which cannot'be treated as easily or at so low a cost with the demulsifying agents heretoforeavailable.

In practising my process, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various waysor by any of the various apparatus now generally 'used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone. or in combination with other demulsifylng procedure, such as the electrical dehydration process. The new composition of matter that is employed as the. demulsifying agent .in my process herein described constitutes the subject matter of my pending application for Patent Serial No. 261,094, filed -March 10, 1939.

Having thus described my invention, what' 'I' now claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising products of the kind-derivable by I esterification reaction between (A) an amine of the formula type:

in which R.COO represents the oxy-acyl radical derived from a monobasic detergent-forming carboxy acid; T represents a hydrogen atom or -a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 8 carbon atoms; n

represents a small whole number whichis less than 10; m represents the numeral 1 or 2; m represents the numeral 1 or ,2, and m" represents the numeral 0 or 1; with the proviso that ml-m+m"=3; and (B). an acidic ester derived by reaction between a polybasic carboxy acid and a hydroxylated ester of a monobasic detergentforming carboxy acid of the kind in which there is at least one hydroxyl radical attached to the alcohol-residue; said acidic ester being characterized by the presence of at least one carboxyl radical.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjectingthe emulsion to the action of a demulsifying agent comprising products of the kind in which R000 represents the oxy-acyl radical derived from a monobasic detergent-forming carboxy' acid; T represents a hydrogen atom or a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacing-a hydrogen atom of the hydroxyl group oi an alkylol radical by the acyl radical of a monobasic'carboxy acid having less than 8 carbon atoms; ClnHzn is an aliphatic radical; n represents a small whole number which is less than 10; m represents the numeral 1 or 2; m" represents the numeral 1 or 2, and m" represents the numeral 0 or 1; with the proviso that m+m'+m"=3; and .(B) an acidic ester derived by reaction between a polybasi carboxy acid and a hydroxylatedester rivable by esterification reaction between (A) an amine of the formula type:

Rhodesia).

in which H.000 represents the oxyacyl radical derived from a fatty acid; T represents a hydrogen atom or a non-hydroxy hydrocarbon radical or the acylated radical obtained by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having less than 8 carbon atoms; CnHLn is an aliphatic radicalm represents a small whole number which is less than 10; m represents the numeral 1 or 2; m represents the numeral 1 or 2, and m" represents the numeral 0 or -1; with the proviso that m+1n'+-m"=3; and (B) an acidic ester derived by reaction between a polybasic carboxy acid and a hydroxylated ester of a monobasic detergent-forming carboxy acid of the kind in which there is at least one bydroxyl radical attached to the alcohol residue;

in which-RG00 represents the oxy-acyl radical derived from a hydroxylated fatty acid; T represents a hydrogen atom or a non-hydroxy hydrocarbon radical or the acylated radical obtaihed by replacing a hydrogen atom of the hydroxyl group of an alkylol radical by the acyl radical of a monobasic carboxy acid having lessthan 8 carbon atoms; CnHza is an aliphatic radical; n represents a small whole number which is less than 10; 111, represents the numeral 1 or 2; m represents the numeral 1 or 2; and m" represents the numeral 0 or 1; with the proviso that m+m'+m"=3; and (B) an acidic ester derived by reaction between a polybasic carboxy acid and a hydroxylated ester of a monobasic detergent-forming carboxy acid of the kind in whichthere is at least one hydroxyl radical at tached to the alcohol residue; said acidic ester being characterized by the presence 0! at least one carboxyl radical.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub- .iecting the emulsion to the action of a demulsitying agent comprising products of the kind.de-

rivable by esteriflcation reaction between (A) in which OHRCOO represents the oxy-acyl radical derived from a hydroxylated fatty acid; 11: represents the numeral 1 or- 2; 111' represents the numeral 1 or 2; with the proviso that m+m'=3; and (B) an acidic ester derived by reaction between a polybasic carboxy acid and a. hydroxylated ester of a monobasic detergent-forming carboxy acid of the kind in which there is at least one hydroxyl radical attached to the alcohol residue; said acidic ester being characterized by the presence of at least one carboxyl radical.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsii'ying agent comprising products of the kind derivable by esterification reaction bemeen (A) in which OHRCOO represents the oxy-acyl radical derived from rlcinoleic acid; m represents the numeral 1 or 2; m represents the numeral 1 or 2; with the proviso that 1n+m'=3; and (B) an acidic ester derived by reaction between a polybasic carboxy acid and a hydroxylated ester of a monobasic detergent-forming carboxy acid of the kind in which there is at least one hydroxyl radical attached to the alcohol residue; said acidic ester being characterized by the presence of at least one carboxyl radical.

7. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsiiying agent comprising products of the kind derivable by esteriflcation reaction between (A) an amine oi the formula type:

in which OERCOO represents the oxy-acyl radical derived from ricinoleic acid; m represents the numeral 1 or 2; m represents the numeral 1 or 2; with the proviso that 1n+m'=3; and (B) an acidic ester derived by reaction between phthalic anhydride and a hydroxylated ester of a monobasic detergent-forming cal-boxy acid of the kind in which there but least one hydromyi radical attached to the. alcohol residue; said acidic ester being characterized by the presence of at least one carboxyl radical.

MELVIN DE GROO'I'I.

CERTIFICATE OF commoner:

Patent no; 2,166,L; L,. I July 13, 19 9,

Imam/DE encore...

It is hereby certified that/error appears in the printed specification the above numbered requiring correction as follows: Page 1, sec- 0nd column, 1121955, for Erection reed reaction; page 5, first col, line 75, in the formula, before OILC H insertaparenthesia; And second colm, line 53, for inclined read. included; and that the said Letters Patentahould be read with this correction therein that the same may conform to the record of the case in the Patent. Officm e Signed and sealed "this 3 d day'cvf' October, A n. 19 9.

1 Henry Van Airedale, (Beel) Acting Commissioner of Paviseinlzea ra zencuol 2,166,151}.

Itfia hereby certified o r appears 11; the printed specification the above numbered pat ant requiring cerrection as follows: vPage 1 sec- 0nd column, Iinej}, for fre ction" read 'reactien; page first column, line, 75, in the female, before "OHQC H 'F inserteparepthesis'; dnd second coimm, line 55,1'or "inclined" read included; and that the said Letters retentshould be read.- with m, cerrecti'on therein that the we may conferm to the record of the case in the Patentv Office; Y Signed and Qeiled 1115 jraaa 'or October, A; n. 19 9.

. I enry Van Arede-le, v

13 1) Acting Commissioner or Patents. 

